CA1265067A - Method for cleaning gases containing condensable components - Google Patents
Method for cleaning gases containing condensable componentsInfo
- Publication number
- CA1265067A CA1265067A CA000490749A CA490749A CA1265067A CA 1265067 A CA1265067 A CA 1265067A CA 000490749 A CA000490749 A CA 000490749A CA 490749 A CA490749 A CA 490749A CA 1265067 A CA1265067 A CA 1265067A
- Authority
- CA
- Canada
- Prior art keywords
- mixture
- solids
- gas
- particulate solids
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Industrial Gases (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Gases containing tar and other condensable components are cleaned by cooling them in a circulating fluidized bed reactor (2) provided with cooling surfaces (8). Into the fluidized bed reactor are led solids separated from the cooled gas in a cyclone separator (3) and other solids.
Tar and other compounds condensate on the solids in a mixing chamber (9) disposed before the cooling surfaces in the reactor.
Gases containing tar and other condensable components are cleaned by cooling them in a circulating fluidized bed reactor (2) provided with cooling surfaces (8). Into the fluidized bed reactor are led solids separated from the cooled gas in a cyclone separator (3) and other solids.
Tar and other compounds condensate on the solids in a mixing chamber (9) disposed before the cooling surfaces in the reactor.
Description
~ ~3~ 7 Method for cleaning gases contalning condensable components The present invention relates to a dry cleaning method for gases containing dust and tar generated by a partial oxida-tion of biomasses, peat or coal and for other gases contain-ing condensable components, in which method the gas is cooled in a fluidized bed reactor provided with cooling surfaces.
The use of solid fuels in applications substituting oil is aggravated by e.g. unorganic compounds (ash) in them and by their slow diffusion combustion which is attributable to the nature of the particles~ A "clean" fuel with a low ash content is often required in process industries (driers, lime sludge rebuxning kilns, production of synthesis gas) for the sake of the quality of the product or for avoiding process troubles. In gas turbines and diesel motors the direct use of solid fuels is restricted by the requirement for total absence of ash and by the slow combustion. Thus it is expedient to bring the fuel into a gaseous condition before exploitation.
Gasifiers based on partial oxidation have originally been simple fixed packed bed/counter-current gasifiers and gas generated by them has been rich in tarlike, organic com-pounds. Gases containing less tar can be generated by performing a parallel-flow gasification. ~ parallel-flow gasification has required a transition from fixed packed bed gasifiers to fluidized bed and suspension gasifiers. In a parallel-flow gasification the proportion of contaminants in the product gas changes so that few tars are generated in proportion to solid, finely divided co~e. The proportion of tar and coke can effectively be influenced by the final temperature of the gas that is, however, restricted by the melting temperature of fluidized material in the fluidized bed reactor. In fluidized bed gasifiers some of the solids .
: , :
.
j5~)~i7 to be gasified flows with the gas and generate tar combina-tions in the whole area of the gasifying reactor. Tar generated near an outlet does not have time to disintergrate into light hydrocarbons, which further increases the tar content of a produc-t gas. To summarize -the stage of the gasification technique today one can say that tar compounds in a product gas form a central restriction for gas applications.
The most usual method for cleaning combustion or synthesis gas is probably the cleaning by means of a liquid, generally water. Water or some other liquid is sprayed into hot or already cooled combustion gas, gas is cooled and cleaned from at least solids and mainly also from tars. Scrubbing is not an efficient method for removing tars since only some tars are water-soluble. Due to capillary action it is impossible to remove the smallest tar drops by scrubbing. In addition to a poor cleaning effect the greatest disadvan-tages of scrubbing are a great power demand, expensive investments and treatment costs of waste waters.
US-patent 4,198,212 shows a gas cleaning method in which coke and gas containing tar generated by coal gasification are led into a fluidized bed cooling device in which the coke cooled by an indirect method forms a fluidized bed. In this fluidized bed tars from the through flowing gas are condensed.
US-patent 2,538,013 shows a method for removing sublimable components fxom gas in a fluidized bed reactor provided with cooling surfaces, in which reactor gas and solids suspended into it are cooled mainly in a cooling surface zone. This provides a risk for contamination.
; "', ` ~",.
.
i5~
An object of the invention is to accomplish a ~as cleaning method which compared with the known method can more easily be controlled according to varying process parameters, and which furthermore, is suitable for removing except tars also other condensable components e.g. natrium and sulphur compounds from gases.
An almost total separation of condensed tars can be accomplished with the method according to ths invention with small investment and running costs and with no cleaning waters that would be detrimental to the environment or would need expensive treatments. The method according to the invention is characterized in that cooling takes place in a circulating bed reactor into which æolids separated from the cooled gas and other solids for controlling the function of the reactor are fed and that the heat capacity flow of these solids is so large that it is able essentially to cool the gas ~0 to the condensation temperature of the condensable components bef~re the gas is brought into contact with the cooling surfaces.
.
The invention will be described in detail in the ~S following with reference to the accompanying drawing.
Gas containing tar to be cooled is led through an inlet .
., ,~' ~, `.
3a ~ i7 1 into a mixing chamber 9 disposed in a lo~er part of a circulating bed reactor 2. Gases leaving the upper part of the reactor are led into a cyclone separator 3 wherefrom some of the solids separated from the gases are recirculated into the lower part of the reactor through a pipe 4. Also new solids, (also re~erred to as "other solids") e.g. sand, are fed into the lower part of the reactor through a pipe 5. The recirculated solids and the new solids thus form what can generally be referred to as a mixture of particulate solids. In case the gas to be cleaned contains sulphur compounds it is expedient to choose a solid that will bind the sulphur as a sulphide. Similarly, if the gas contains sodium compounds, it is expedient to select the mixture of particulate material such that it contains sodium binding particles.
^~ ~
~ ' . . .
~ . . .
~ ~ ~ , ....... . . .
Some of the solids separated from the gases are discharged through a pipe 6 for further processing. The gas cleaned from solids is discharged throwgh a central pipe 7 in the separator.
In the fluidized bed reactor the gases with their solids are cooled by means of cooling surfaces 8 to such a temperature that the main part of the tar compounds condense on the solids already in the mixing chamber 9.
The amount of solids flowing through the fluidized bed reactor is controlled by changing the solids flow fed through the pipe 5 and discharged through the pipe ~ by means of of rotary feeders 10 and 11. There is no sluice valve or other blocking device in the return pipe 4. Air nozzles can be installed in the pipe by means of which the return flow can be controlled. The temperature and the dwelling time in the reactor are chosen to maximize the cleaning effect.
By means of the additive, i.e. the solids introduced through pipe 5, by changing the grain size and quality of the additive (e.g. particle density), the controllability can be improved and also the heat transfer to the cooling surfaces somewhat influenced.
In order to secure a long dwelling time in the mixing chamber and a large contact area between the circulating solids and the solids to be cooled the free cross section of the flow in the mixing chamber is at least twice the one in the cooling zone of the reactor where the cooling surfaces 8 are disposed.
The flow velocity of the gas in the cooling zone is preferably 2-10 m/s and at the most half of this in the mixing chamber.
. : ~
, ~ ~ , ,,, . . :
:' ' :
: - :. , .
i7 The solids density of the suspension in the reactor is preferably 2-20 kg/m3.
The invention is not limited to the above embodiment but it can be modified and applied within the scope of the claims. In some cases the cooling effect of the solids flow through the pipe 5 can be so large that use of the cooling surfaces 8 becomes unnecessary.
The use of solid fuels in applications substituting oil is aggravated by e.g. unorganic compounds (ash) in them and by their slow diffusion combustion which is attributable to the nature of the particles~ A "clean" fuel with a low ash content is often required in process industries (driers, lime sludge rebuxning kilns, production of synthesis gas) for the sake of the quality of the product or for avoiding process troubles. In gas turbines and diesel motors the direct use of solid fuels is restricted by the requirement for total absence of ash and by the slow combustion. Thus it is expedient to bring the fuel into a gaseous condition before exploitation.
Gasifiers based on partial oxidation have originally been simple fixed packed bed/counter-current gasifiers and gas generated by them has been rich in tarlike, organic com-pounds. Gases containing less tar can be generated by performing a parallel-flow gasification. ~ parallel-flow gasification has required a transition from fixed packed bed gasifiers to fluidized bed and suspension gasifiers. In a parallel-flow gasification the proportion of contaminants in the product gas changes so that few tars are generated in proportion to solid, finely divided co~e. The proportion of tar and coke can effectively be influenced by the final temperature of the gas that is, however, restricted by the melting temperature of fluidized material in the fluidized bed reactor. In fluidized bed gasifiers some of the solids .
: , :
.
j5~)~i7 to be gasified flows with the gas and generate tar combina-tions in the whole area of the gasifying reactor. Tar generated near an outlet does not have time to disintergrate into light hydrocarbons, which further increases the tar content of a produc-t gas. To summarize -the stage of the gasification technique today one can say that tar compounds in a product gas form a central restriction for gas applications.
The most usual method for cleaning combustion or synthesis gas is probably the cleaning by means of a liquid, generally water. Water or some other liquid is sprayed into hot or already cooled combustion gas, gas is cooled and cleaned from at least solids and mainly also from tars. Scrubbing is not an efficient method for removing tars since only some tars are water-soluble. Due to capillary action it is impossible to remove the smallest tar drops by scrubbing. In addition to a poor cleaning effect the greatest disadvan-tages of scrubbing are a great power demand, expensive investments and treatment costs of waste waters.
US-patent 4,198,212 shows a gas cleaning method in which coke and gas containing tar generated by coal gasification are led into a fluidized bed cooling device in which the coke cooled by an indirect method forms a fluidized bed. In this fluidized bed tars from the through flowing gas are condensed.
US-patent 2,538,013 shows a method for removing sublimable components fxom gas in a fluidized bed reactor provided with cooling surfaces, in which reactor gas and solids suspended into it are cooled mainly in a cooling surface zone. This provides a risk for contamination.
; "', ` ~",.
.
i5~
An object of the invention is to accomplish a ~as cleaning method which compared with the known method can more easily be controlled according to varying process parameters, and which furthermore, is suitable for removing except tars also other condensable components e.g. natrium and sulphur compounds from gases.
An almost total separation of condensed tars can be accomplished with the method according to ths invention with small investment and running costs and with no cleaning waters that would be detrimental to the environment or would need expensive treatments. The method according to the invention is characterized in that cooling takes place in a circulating bed reactor into which æolids separated from the cooled gas and other solids for controlling the function of the reactor are fed and that the heat capacity flow of these solids is so large that it is able essentially to cool the gas ~0 to the condensation temperature of the condensable components bef~re the gas is brought into contact with the cooling surfaces.
.
The invention will be described in detail in the ~S following with reference to the accompanying drawing.
Gas containing tar to be cooled is led through an inlet .
., ,~' ~, `.
3a ~ i7 1 into a mixing chamber 9 disposed in a lo~er part of a circulating bed reactor 2. Gases leaving the upper part of the reactor are led into a cyclone separator 3 wherefrom some of the solids separated from the gases are recirculated into the lower part of the reactor through a pipe 4. Also new solids, (also re~erred to as "other solids") e.g. sand, are fed into the lower part of the reactor through a pipe 5. The recirculated solids and the new solids thus form what can generally be referred to as a mixture of particulate solids. In case the gas to be cleaned contains sulphur compounds it is expedient to choose a solid that will bind the sulphur as a sulphide. Similarly, if the gas contains sodium compounds, it is expedient to select the mixture of particulate material such that it contains sodium binding particles.
^~ ~
~ ' . . .
~ . . .
~ ~ ~ , ....... . . .
Some of the solids separated from the gases are discharged through a pipe 6 for further processing. The gas cleaned from solids is discharged throwgh a central pipe 7 in the separator.
In the fluidized bed reactor the gases with their solids are cooled by means of cooling surfaces 8 to such a temperature that the main part of the tar compounds condense on the solids already in the mixing chamber 9.
The amount of solids flowing through the fluidized bed reactor is controlled by changing the solids flow fed through the pipe 5 and discharged through the pipe ~ by means of of rotary feeders 10 and 11. There is no sluice valve or other blocking device in the return pipe 4. Air nozzles can be installed in the pipe by means of which the return flow can be controlled. The temperature and the dwelling time in the reactor are chosen to maximize the cleaning effect.
By means of the additive, i.e. the solids introduced through pipe 5, by changing the grain size and quality of the additive (e.g. particle density), the controllability can be improved and also the heat transfer to the cooling surfaces somewhat influenced.
In order to secure a long dwelling time in the mixing chamber and a large contact area between the circulating solids and the solids to be cooled the free cross section of the flow in the mixing chamber is at least twice the one in the cooling zone of the reactor where the cooling surfaces 8 are disposed.
The flow velocity of the gas in the cooling zone is preferably 2-10 m/s and at the most half of this in the mixing chamber.
. : ~
, ~ ~ , ,,, . . :
:' ' :
: - :. , .
i7 The solids density of the suspension in the reactor is preferably 2-20 kg/m3.
The invention is not limited to the above embodiment but it can be modified and applied within the scope of the claims. In some cases the cooling effect of the solids flow through the pipe 5 can be so large that use of the cooling surfaces 8 becomes unnecessary.
Claims (14)
1. A method for cleaning gases containing condensable components in which the gases are cooled in a fluidized bed reactor provided with cooling surfaces, the cooling takes place in a circulating bed reactor into which a mixture of particulate solids is fed, said mixture comprising solids separated from the cooled gas and other solids, for controlling the operation of the reactor the heat capacity flow of said mixture being so large that it is able essentially to cool the gas to the condensation temperature of the condensable components before the gas is brought into contact with the cooling surfaces.
2. A method according to claim 1 characterized in that the flow velocity of the gas in a mixing chamber where the gas is brought into contact with the solids is at the most half of the velocity in the cooling zone provided with cooling surfaces.
3. A method according to claim 1 or 2, characterized in that the gas flow velocity in the cooling zone is 2-10 m/s.
4. A method according to claim 1, characterized in that the density of the mixture of particulate solids contained in a suspension in the reactor is 2-20 kg/m3.
5. A method according to claim 1, characterized in that the mixture of particulate solids is sand.
6. A method according to claim 1, characterized in that the mixture of particulate solids includes solid particles of a sulphur binding substance.
7. A method according to claim 1, characterized in that the mixture of particulate solids includes solid particles of a sodium binding substance.
8. A method according to claim 2, further comprising one or more of the following features:
the gas flow velocity in the cooling zone is 2-10m/s;
the solids density of the mixture of particulate solids contained in a suspension in the reactor is 2-20 kg/m3.
the gas flow velocity in the cooling zone is 2-10m/s;
the solids density of the mixture of particulate solids contained in a suspension in the reactor is 2-20 kg/m3.
9. A method according to claim 2, characterized in that the mixture of particulate solids for controlling the function of the reactor is sand.
10. A method according to claim 2, characterized in that the mixture of particulate solids is sulphur binding.
11. A method according to claim 2, characterized in that the mixture of particulate solids is sodium binding.
12. A method according to claim 8, characterized in that the mixture of particulate solids is sand.
13. A method according to claim 8, characterized in that the mixture of particulate solids includes solid particles of a sulphur binding substance.
14. A method according to claim 8, characterized in that the mixture of particulate solids includes solid particles of a sodium binding substance.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI843606A FI76707C (en) | 1984-09-14 | 1984-09-14 | Process for the purification of gases containing condensable components |
| FI843606 | 1984-09-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1265067A true CA1265067A (en) | 1990-01-30 |
Family
ID=8519606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000490749A Expired - Fee Related CA1265067A (en) | 1984-09-14 | 1985-09-13 | Method for cleaning gases containing condensable components |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5019137A (en) |
| EP (1) | EP0228373B1 (en) |
| BR (1) | BR8507243A (en) |
| CA (1) | CA1265067A (en) |
| DE (1) | DE3572365D1 (en) |
| ES (1) | ES8608568A1 (en) |
| FI (1) | FI76707C (en) |
| PT (1) | PT81123B (en) |
| SU (1) | SU1639434A3 (en) |
| WO (1) | WO1986001822A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI82612C (en) * | 1987-05-08 | 1991-04-10 | Ahlstroem Oy | Process and apparatus for treating process gases |
| DE3724947A1 (en) * | 1987-07-28 | 1989-02-16 | Uhde Gmbh | METHOD AND DEVICE FOR COOLING RAW GAS FROM A PARTIAL OXIDATION OF CARBONATED MATERIAL |
| US5213587A (en) * | 1987-10-02 | 1993-05-25 | Studsvik Ab | Refining of raw gas |
| US5330562A (en) * | 1993-03-12 | 1994-07-19 | Medx, Inc. | Fluidized bed scrubber for use in gas cleaning system |
| FI96321C (en) * | 1993-06-11 | 1996-06-10 | Enviropower Oy | Method and reactor for treating process gas |
| US5464597A (en) * | 1994-02-18 | 1995-11-07 | Foster Wheeler Energy Corporation | Method for cleaning and cooling synthesized gas |
| US5503811A (en) * | 1994-09-19 | 1996-04-02 | Ahluwalia; R. K. | Method for removing metal vapor from gas streams |
| US5567228A (en) * | 1995-07-03 | 1996-10-22 | Foster Wheeler Energy Corporation | System for cooling and cleaning synthesized gas using ahot gravel bed |
| FI112665B (en) * | 1999-05-14 | 2003-12-31 | Fortum Oil & Gas Oy | Process and plant for gasification of carbonaceous material |
| NL1030189C2 (en) * | 2005-10-13 | 2007-04-16 | Stichting Energie | Biogas purification apparatus, contains bed comprising carbon particles and base particles of a material other than carbon |
| JP5265277B2 (en) * | 2008-09-08 | 2013-08-14 | 本田技研工業株式会社 | Desulfurization equipment |
| CN102585916B (en) * | 2011-12-29 | 2014-11-26 | 武汉凯迪工程技术研究总院有限公司 | Biomass synthesized gas negative pressure purifying process method and system configuration for producing oil |
| CN102728181B (en) * | 2012-07-23 | 2014-05-07 | 东南大学 | Fluidized bed jetting adsorbent smoke demercuration device and method thereof |
| EP2888033B1 (en) | 2012-08-27 | 2019-11-27 | Southern Company | Multi-stage circulating fluidized bed syngas cooling |
| CN105148631B (en) * | 2015-10-14 | 2017-05-24 | 成都市智联环境保护设备有限公司 | Dust remover provided with heating jacket |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2583013A (en) * | 1945-10-26 | 1952-01-22 | Standard Oil Dev Co | Condensation of sublimable material |
| US3443360A (en) * | 1967-10-12 | 1969-05-13 | Du Pont | Fluid bed cooler for gas separation |
| BE759736A (en) * | 1969-12-02 | 1971-06-02 | Exxon Research Engineering Co | PURIFICATION OF FUELS; |
| DE2056096B2 (en) * | 1970-11-14 | 1978-09-28 | Metallgesellschaft Ag, 6000 Frankfurt | Process for the separation of hydrogen fluoride from gases |
| US4135893A (en) * | 1974-07-08 | 1979-01-23 | Cogas Development Company | Mixing method and device |
| US4078041A (en) * | 1976-03-01 | 1978-03-07 | Rexnord Inc. | Electrofluidized bed gas purification arrangement and method |
| US4120668A (en) * | 1976-06-21 | 1978-10-17 | Pullman Incorporated | Method for removing entrained melt from a gaseous stream |
| US4198212A (en) * | 1977-05-24 | 1980-04-15 | The Lummus Company | Coal gasification effluent treatment |
| DE2910830B1 (en) * | 1979-02-16 | 1980-07-24 | Alusuisse | Device for extracting solid aluminum chloride |
| DE3102819A1 (en) * | 1980-01-29 | 1982-02-18 | Babcock-Hitachi K.K., Tokyo | METHOD FOR RECOVERY OF HEAT IN COAL GASIFICATION AND DEVICE THEREFOR |
| US4303127A (en) * | 1980-02-11 | 1981-12-01 | Gulf Research & Development Company | Multistage clean-up of product gas from underground coal gasification |
| US4372937A (en) * | 1980-04-18 | 1983-02-08 | Phillips Petroleum Company | Waste heat recovery |
| DE3023480A1 (en) * | 1980-06-24 | 1982-01-14 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR HOT DESULFURING FUEL OR REDUCING GASES |
| JPS57179289A (en) * | 1981-04-28 | 1982-11-04 | Agency Of Ind Science & Technol | Recovering method of heat from gasified product of hydrocarbon |
| FI64997C (en) * | 1981-11-23 | 1986-01-08 | Ahlstroem Oy | FOERFARANDE FOER TILLVARATAGANDE AV VAERME UR GASER INNEHAOLLANDE VAERMEYTOR NEDSMUTSANDE AEMNEN |
| US4474584A (en) * | 1983-06-02 | 1984-10-02 | Texaco Development Corporation | Method of cooling and deashing |
-
1984
- 1984-09-14 FI FI843606A patent/FI76707C/en not_active IP Right Cessation
-
1985
- 1985-08-30 DE DE8585904254T patent/DE3572365D1/en not_active Expired
- 1985-08-30 BR BR8507243A patent/BR8507243A/en not_active IP Right Cessation
- 1985-08-30 WO PCT/FI1985/000074 patent/WO1986001822A1/en active IP Right Grant
- 1985-08-30 EP EP85904254A patent/EP0228373B1/en not_active Expired
- 1985-09-10 ES ES546827A patent/ES8608568A1/en not_active Expired
- 1985-09-13 PT PT81123A patent/PT81123B/en unknown
- 1985-09-13 CA CA000490749A patent/CA1265067A/en not_active Expired - Fee Related
-
1987
- 1987-03-09 SU SU874202091A patent/SU1639434A3/en active
-
1990
- 1990-04-12 US US07/508,497 patent/US5019137A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3572365D1 (en) | 1989-09-21 |
| FI843606L (en) | 1986-03-15 |
| SU1639434A3 (en) | 1991-03-30 |
| FI843606A0 (en) | 1984-09-14 |
| ES8608568A1 (en) | 1986-07-16 |
| US5019137A (en) | 1991-05-28 |
| PT81123A (en) | 1985-10-01 |
| EP0228373A1 (en) | 1987-07-15 |
| ES546827A0 (en) | 1986-07-16 |
| EP0228373B1 (en) | 1989-08-16 |
| FI76707B (en) | 1988-08-31 |
| WO1986001822A1 (en) | 1986-03-27 |
| FI76707C (en) | 1988-12-12 |
| PT81123B (en) | 1987-10-20 |
| BR8507243A (en) | 1987-10-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |